US3152089A - Catalyst for production of olefin polymers - Google Patents

Catalyst for production of olefin polymers Download PDF

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Publication number
US3152089A
US3152089A US144857A US14485761A US3152089A US 3152089 A US3152089 A US 3152089A US 144857 A US144857 A US 144857A US 14485761 A US14485761 A US 14485761A US 3152089 A US3152089 A US 3152089A
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catalyst
metal
halide
peroxide
range
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Nowlin Gene
Harold D Lyons
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Phillips Petroleum Co
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Phillips Petroleum Co
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Priority to NL94901D priority Critical patent/NL94901C/xx
Priority to IT564176D priority patent/IT564176A/it
Priority to NL213365D priority patent/NL213365A/xx
Priority claimed from US556482A external-priority patent/US3024227A/en
Priority to GB39426/56A priority patent/GB832083A/en
Priority to FR1169630D priority patent/FR1169630A/fr
Priority to CH361919D priority patent/CH361919A/fr
Application filed by Phillips Petroleum Co filed Critical Phillips Petroleum Co
Priority to US144857A priority patent/US3152089A/en
Publication of US3152089A publication Critical patent/US3152089A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • This invention relates to a novel catalyst for use in a process for polymerizing olefins.
  • Reactions for polymerizing olefins are well known in the art and are generally carried out in the presence of catalysts.
  • One class of catalysts which has been used in the polymerization of monoolefins, particularly ethylene, is organornetal compounds, for example triethylaluminum, and the polymers which have been obtained in accordance with this method are generally liquid or low molecular weight solid polymers. Frequently, the polymers obtained are dimers or trimers of the olefin charged.
  • Such uses cannot be made of the lower molecular weight polymers, for example, a polymer having a molecular weight of about 1000, since a polymer of this molecular weight is a wax-like material.
  • a still further object is to produce high molecular weight solid polymers of olefins, such as ethylene.
  • a catalyst composition comprising (1) a metal halide selected from the group consisting of halides of titanium, zirconium, hafnium and germaninum (2) a peroxide corresponding to the formula R'OOR', wherein R is hydrogen, an alkyl, aralkyl, alkaryl, cycloalkyl, acyl, alkyne or aryl radical, and (3) at least one component selected from the following: (a) an organometal halide corresponding to the formula R MX wherein R is a saturated acylic hydrocarbon radical, a saturated cyclic hydrocarbon radical, an aromatic hydrocarbon radical, or combination of these radicals, wherein M is a metal selected from the group consisting of aluminum, gallium, indium, thallium, and beryllium and wherein X is a halogen, and wherein
  • the improvement obtained when polymerizing an olefin in the presence of our novel catalyst is, firstly, that polymers of much higher molecular weight possessing very high impact strength and other desirable characteristics can be obtained than is true when certain of the prior art catalysts have been employed, and secondly, the polymerization reaction, particularly or ethylene, can be initiated and carried out at considerably lower temperatures and pressures than are necessary when employing the catalysts and the processes of the prior art.
  • the metal halide component of our catalyst system comprises the halides of the metals titanium, zirconium, hafnium and germanium.
  • metal halides which can be used include titanium dichloride, titanium trichloride, titanium tetrachloride, titmum dibromide, titanium tribromide, titanium tetrabromide, titanium diiodide, titanium triiodide, titanium tetraiodide, titanium trifluoride, titanium tetrafluoride, zirconium dichloride, Zirconium trichloride, zirconium tetrachloride, zirconium di bromide, zirconium tribromide, Zirconium tetrabromide, zirconium tetraiodide, zirconium tetrafiuoride, hafnium trichloride, hafnium tetrachloride, hafnium triiodide, hafnium t
  • our novel catalyst comprises a peroxide corresponding to the formula ROOR, wherein R is hydrogen, an alkyl, aralkyl, alkaryl, cycloalkyl, acyl, alkyne, or aryl radical. These radicals may each contain from 1 to 20, inclusive, preferably not more than 10, carbon atoms.
  • peroxides which can be used include hydrogen peroxide, methyl hydroperoxide, isopropyl hydroperoxide, tert-butyl hydroperoxide, cyclohexyl hydroperoxide, a,a-dimethyl-p-isopropylbenzyl hydroperoxide, dimethyl peroxide, di-n-propyl peroxide, di-tert-butyl peroxide, methyl ethyl peroxide, B-methyl-S-hydroperoxyl-butyne, Z-methyl-B-butynyl hydroperoxide, bis(2-methyl-3-butynyl) peroxide, dibenzoyl peroxide, diacetyl peroxide, dipropionyl peroxide, a,a-dinaphthyl peroxide, peroxyformic acid, peroxyacetic acid, peroxybutyric acid, peroxybe-nzoic acid, peroxycinnamic acid, diperoxyterephthal
  • our catalyst comprises at least one organometal halide corresponding to the formula R MX wherein R is a saturated acyclic hydrocarbon radical, a saturated cyclic hydrocmbon radical, an aromatic hydrocarbon radical, or mixtures of these radicals, wherein M is a metal selected from the group consisting of aluminum, gallium, indium, thallium and beryllium, and wherein X is a halogen.
  • R is a saturated acyclic hydrocarbon radical, a saturated cyclic hydrocmbon radical, an aromatic hydrocarbon radical, or mixtures of these radicals
  • M is a metal selected from the group consisting of aluminum, gallium, indium, thallium and beryllium
  • X is a halogen.
  • the x and y are integers and the sum of x and y is equal to the valence of the metal M.
  • X can be any of the halogens, including chlorine, bromine, iodine and fluorine.
  • the saturated acyclic hydrocarbon radicals, saturated cyclic hydrocarbon radicals, and aromatic hydrocarbon radicals which can be substituted for R in the formula include hydrocarbon radicals having up to about 20 carbon atoms each. Radicals having 10 carbon atoms or less are preferred since the resulting catalyst composition has a greater activity for initiating the polymerization of olefins.
  • Mixtures of one or more of these-organometal halide components, such as a mixture of ethylaluminum dichloride and diethylaluminum chloride, can be used in our catalyst composition.
  • Specific examples of other organornetal halides is lithium aluminum hydride.
  • CH AICI CH AlCl, C H AlCl z slz e sh a 1'r 2, '(c H-fl GaF, (C H GaCl (cyclohexane derivative), (C H )GaBr (benzene derivative), C H GaBr (C H GaF, (C H InCl (benzene derivative), C H InF (C H QInBr (cyclohexane derivative), C17H35B$L CH BeBr,
  • our catalyst comprises a mixture of one or more of the metal halides and one or more of the peroxides described above and a mixture of an organic halide and a free or elemental metal.
  • organic halides include chloro-, bromo-, iodoand fluoro-substituted organic halides, and can be mono-, di-, trior tetrasubstituted organic halides.
  • the 'class of halides defined as monohalogen-substituted hydrocarbons having a maximum carbon chain length of not greater than 8 carbon atoms are preferred since they are more easily handled in a commercial operation and are active to initiate the polymerization of olefins in the catalyst composition of this invention.
  • the organic halide which is used in the catalyst is a lower alkyl monohalide having a maximum carbon chain length of not greater than '8 carbon atoms. Examples of these organic halides which can be used in the catalyst are ethyl bromide, propylchloride, butyl iodide and pentyl fluoride.
  • 1,2-dibromoethane, 1,3-dibromopropane, 1,2,3-tribromopropane, 1,2,3-trichloropropane, l,l-difluoroethane, and 1,4-diiodobutane examples are 1,2-dibromoethane, 1,3-dibromopropane, 1,2,3-tribromopropane, 1,2,3-trichloropropane, l,l-difluoroethane, and 1,4-diiodobutane.
  • Other acyclic and cyclic halides as well as aromatic halides can be employed also.
  • Examples of these are 1,3-dichlorocyclohexane, benzyl chloride, 1,4-dichlorobenzene, l- -bromodecane, l-chlorododecane, 2-chlorooctane, 2-chloro- 4-methyloctane, cyclopentyl chloride, 1-chloro-3-phenylpropane, 1-bromo-3-phenylhexane, cyclohexyl chloride and phenyl chloride.
  • alkenyl halides such as allyl bromide
  • alkynyl halides such as propargyl chloride
  • the metals which are employed in admixture with an organic halide include one or more of so- .dium, potassium, lithium, rubidium, cesium, beryllium,
  • the metals are usually used in the 'form of shavings, turnings or finelydivided powder.
  • Various mixtures of combinations of the above-mentioned organic halides and-metals can be employed in the catalyst composition of this invention.
  • M is an alkali metal, including sodium, potassium, lithium, rubidium and 'cesium
  • M" is a metal selected from the group consisting 'of aluminum, gallium, indium and thallium
  • m is equal to the sum of the valences of the two metals.
  • tively low reaction temperatures and pressures are the following: a mixture of titanium tetrachloride and benzoyl peroxide with an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chloride; a mixture of zirconium tetrachloride and benzoyl peroxide with an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chloride; a mixture of titanium tetrachloride, benzoyl peroxide and lithium aluminum hydride; a mixture of titanium trichloride and benzoyl peroxide with an approximately equimolar mixture of ethylaluminum dichlorideand diethylaluminum chloride; a mixture of titanium tetrachloride and di-tert-butyl peroxide with an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chloride; and
  • the amount of the catalyst composition of this invention which is used in the polymerization of olefins can vary over a Wide range. Relatively small amounts of the catalyst provide the desired activating effect when the polymerization reaction is carried out as a batch process with continuous addition of the olefin as the polymerization reaction occurs. As much as 50 to 2000 grams of polymer can be obtained per gram of catalyst composi-' tion utilized in the reaction. When a continuous flow system is employed, the concentration of the total catalyst composition is usually in the range from 0.01 weight percent to 1.0 weight percent, or higher.
  • the ratio of the amounts of peroxideto metal halide will generally be in the range of 0.05 to 50, preferably 0.2 to 3 mols peroxide per mol of metal halide.
  • the ratio of the amounts of organometal halide to metal halide will usually be in the range of 0.05 to 50, preferably 0.2 to 3 mols of organomental halide per mol of metal halide.
  • the ratio of the amounts of organic halide, metal and metal halide will be in the range of 0.02 to 50 mols of the organic halide per mol of the metal halide and from.
  • a preferred ratio is from 0.2 to 3 mols of organic halide per mol of metal halide and from 0.2 to 3 mols of metal per mol of the metal halide.
  • the ratio of the amounts of the complex hydride to metal halide will generally be in the range of 0.05 to 50, preferably 0.2 to 3, mols of complex hydride per mol of metal halide;
  • the materials which are polymerized with the novel catalyst composition of this invention can be defined broadly as polymerizable hydrocarbons.
  • the preferred class of polymerizable hydrocarbons used is aliphatic l-olefins having up to and includingS carbon atoms per molecule.
  • the normal l-olefin, ethylene has been found to polymerize to a polymer thereof upon being contacted with the catalyst composition of. this invention at lower tempertures and pressures than have been used in the processes of the prior are mentioned above.
  • Examples of other polymerizable hydrocarbons which can be used in hexene and l-octene. Branched chain olefins can also tuted and 1,2-dialkyl-substituted ethylenes can also .be
  • Examples of the diand polyolefins in which the double bonds are in non-conjugated positions and which can be used in accordance with this invention are 1,5-hexadiene, 1,4-pentadiene and 1,4,7-octatriene. Cyclic olefinscan also be used, such as cyclohexene. of the foregoing polymerizable hydrocarbons can be po- Mixtures Also, 1,l-dialkyl-substi-.
  • conjugated dienes which can be used include 1,3-butadiene, 2-methyl-l,3-butadiene, 2,3-dirnethyl-1,3-butadiene, 2-rnethyl-1,3-pentadiene, chloroprene, l-cyanobutadiene, 2,3 dimethyl-l,3-pentadiene, 2-methyl-3-ethyl-1,3-pentadiene, Z-methoxybutadiene, Z- henylbutadiene, and the like.
  • the temperature can be varied over a rather broad range, however, such as from 250 F. and below to 500 F. and above.
  • the preferred temperature range is from 50 to 300 F.
  • pressures ranging from atmospheric and below up to 30,000 p.s.i.g. or higher can be employed, a pressure from atmospheric to 1000 p.s.i.g. is usually preferred with a pressure in the range of 100 to 700 p.s.i.g. being even more desirable.
  • Suitable diluents for use in the polymerization process are paraffins, cycloparatfins and/ or aromatic hydrocarbons which are relatively inert, non-deleterious and liquid hexane and methylcyclohexane, and aromatic diluents, under the conditions of the process.
  • the lower molecular weight alkanes, such as propane, butane, and pentane are especially useful when the process is carried out at low temperatures.
  • the higher molecular weight parafins and cycloparafiins such as isooctane, cyclohexane and methylcyclohexane, and aromatic diluents, such as benzene, toluene and the like, can also be used, particularly when operating at higher temperatures.
  • Aromad hydrocarbons such as halogenated aromatics, halogenated paraifms, halogenated cycloparaffins and the like, are also useful as diluents. Mixtures of any two or more of the above-named diluents can also be employed in the process of this invention.
  • the process utilizing the catalyst of this invention can be carried out as a batch process by pressuring the olefin into a reactor containing the catalyst and diluent, if the latter is used. Also, the process can be carried out continuously by maintaining the above-described concentrations of reactants in the reactor for a suitable residence time.
  • the residence time used in a continuous process can vary widely, since it depends to a great extent upon the temperature at which the process is carried out.
  • the residence time also varies with the specific olefin that is polymerized. However, the residence time for the polymerization of aliphatic monoolefins, within the preferred temperature range of 50 to 300 F., falls within the range of one second to an hour or more.
  • the time for the reaction can also vary widely, such as up to 24 hours or more.
  • the catalyst components In charging the catalyst components to the'reaction vessel, it is preferred to operate so as to ensure that the peroxide is not present in the reaction vessel with the organometal halide, the mixture of an organic halide and a metal and/ or the complex hydride unless the metal halide'is also included in the reaction mixture. In this regard it is desirable to mix the metal halide and the peroxide before charging or to charge these two components simultaneously.
  • any excess olefin is vented and the contents of the reactor, including the solid polymer swollen with diluent, are then treated to inactivate the catalyst and remove the catalyst residues.
  • the inactivation of the catalyst can be accomplished by washing with an alcohol, water or other suitable material.
  • the catalyst inactivating treatment also removes a major proportion of the catalyst residues while in other cases it may be necessary to treat the polymer with an acid, base or other suitable material in order to effect the desired removal of the catalyst residues.
  • the treatment of the polymer may be carried out in a comminution zone, such as a Waring Blendor, so that a finely divided polymer is thereby provided.
  • the polymer is then separated from the diluent and treating agents, e.g., by decantation or absorption, after which the polymer is dried.
  • the diluent and treating agents can be separated by any suitable means, e.g., by fractional distillation, and reused in the process.
  • EXAMPLE I Ethylene was polymerized in a 2700 cubic centimeter stainless steel reactor in accordance with the procedure described hereinbelow.
  • a dark brown polymer was recovered which immediately turned white upon contact with methyl alcohol.
  • the polymer was placed in a Waring Blendor along with about 500 cubic centimeters of methyl alcohol and comminuted-at speeds ranging from 8000 to 16,000 r.p.m.
  • the polymer was then filtered and placed on porcelain dishes in a vacuum oven and dried for 24 hours at 75 C. Approximately 50 grams of polymer were obtained.
  • the inherent viscosity was obtained at 130 C., using a solution of 0.2 gram of polymer per 100 milliliters of tetralin.
  • EXAMPLE 111 Ethylene was polymerized in a 1200 cubic centimeter stainless, steel rocking autoclave in the presence of a catae -lyst..consisting of a mixture of 3.55 grams of titanium,
  • diethylaluminum chloride and ethylaluminum dichloride 4 grams of a mixture of diethylaluminum chloride and ethylaluminum dichloride.
  • ture of diethylaluminum chloride and ethylaluminum dichloride was prepared in accordance with the procedure described hereinafter.
  • cubic centimeters of benzene (dried over sodium) and charged to the autoclave while maintaining the autoclave under a nitrogen atmosphere.
  • the ethylene was passed through a purification system to remove oxygen, carbon dioxide and water vapor prior to entering the autoclave.
  • the purification system comprised a pyrogallol solution, a sodium hydroxide solution and drying agents. The ethylene was charged to the autoclave while maintaining the catalyst and diluent at atmospheric temperature.
  • the polymerization of the ethylene was immediately initiated, and as the addition of ethylene continued the temperature of the reaction mixture increased rapidly to 175 F.
  • the ethylene was passed into the autoclave as rapidly as the limitations of the purification system would permit. Maximum pressure reached in the autoclave was 300 p.s.i.g.
  • the bomb was opened, and a polymer of ethylene was present as a suspension in the benzene solution.
  • One hundred cubic centimeters of butyl alcohol was added to the autoclave to The solid polymer was filtered from the benzene-alcohol mixture and then washed with isopropyl alcohol. After filtering the polymer from the isopropyl alcohol, it is dried overnight in a vacuum oven at about 140 F. About grams of polyethylene was obtained.
  • the mixture of diethylaluminum chloride and ethylaluminum dichloride was prepared by placing 150 grams of aluminum shavings in a flask fitted with a reflux condenser and heated to about 70 C. A trace of iodine was added to the flask to act as a catalyst, and ethyl chloridewas charged to the flask in liquid phase. The temperature of the reaction mixture was maintained in the range of to C. during the addition of the ethyl chloride, and the reaction mixture was maintained under a nitrogen atmosphere. When substantially all ofthe aluminum shavings had reacted with the ethyl chloride, the liquid product was removed from the flask and fractionally distilled at 4.5 millimeters of mercury pressure in a packed distillation column.
  • a catalyst composition which forms on mixing materials comprising (1) a metal halide selected from the group consisting of halides of titanium, zirconium, hafnium and germanium, (2) a peroxide corresponding to the formula ROOR, wherein R is a member selected from the group consisting of hydrogen, alkyl, aralk-yl, alkaryl, cycloalkyl, acyl, alkyne and aryl radicals, and (3) an organornetal halide corresponding to the formula R MX wherein R is a member selected from the group consisting of a saturated acyclic hydrocarbon radical, a saturated cyclic hydrocarbon radical, an aromatic hydrocarbon radical and combinations of these radicals, M is a metal selected from the group consisting of aluminum, gallium, indium, thallium and beryllium, and X is a halogen, and wherein x and y are integers, the sum of x and y being equal to the valence of the metal M, the amount of said peroxid
  • a catalyst composition which forms on mixing materials consisting essentially of titanium tetrachloride, benzoyl peroxide, and an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chloride, the amount of said benzoyl peroxide being in the range of 0.05 to 50 mols per mol of said titanium tetrachloride and the amount of said equimolar mixture being in the rangeof 0.05 to mols per mol of said titanium tetrachloride.
  • a catalyst composition which forms on mixing materials consisting essentially of Zirconium tetrachloride, benzoyl peroxide, and an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chloride, the amount of said benzoyl peroxide being in the range of 0.05 to 50 mols per mol of said zirconium tetra chloride and the amount of said equimolar mixture being in the range of 0.05 to 50 mols per mol of said zirconium tetrachloride.
  • a catalyst composition which forms on mixing materials consisting essentially of titanium trichloride, ben zoyl peroxide, and an approximately equimolar mixture of ethylaluminum dichloride and diethylaluminum chlo ride, the amount of said benzoyl peroxide being in the range of 0.05 to 50 mols per mol of said titanium trichloride and the amount of said equimolar mixture being in the range of 0.05 to 50 mols per mol of said titanium trichloride.
  • a catalyst composition which forms on mixing materials consisting essentially of titanium tetrachloride, ditert-butyl peroxide, and an approximate equimolar mixture of ethylaluminum dichloride and diethylalurninum chloride, the amount of said di'tert-butyl peroxide being in the range of 0.05 to 50 mois per mol of said titanium tetrachloride and the amount of said equimolar mixture being in the range of 0.05 to 50 mols per mol of said titanium tetrachloride.

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  • Chemical & Material Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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US144857A 1955-12-30 1961-10-13 Catalyst for production of olefin polymers Expired - Lifetime US3152089A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
IT564176D IT564176A (enrdf_load_stackoverflow) 1955-12-30
NL213365D NL213365A (enrdf_load_stackoverflow) 1955-12-30
NL94901D NL94901C (enrdf_load_stackoverflow) 1955-12-30
FR1169630D FR1169630A (fr) 1955-12-30 1956-12-28 Procédé de polymérisation des hydrocarbures polymérisables et catalyseur utilisé dans ce procédé
GB39426/56A GB832083A (en) 1955-12-30 1956-12-28 Process and catalyst for polymerization of polymerizable hydrocarbons
CH361919D CH361919A (fr) 1955-12-30 1956-12-29 Procédé de polymérisation des hydrocarbures polymérisables
US144857A US3152089A (en) 1955-12-30 1961-10-13 Catalyst for production of olefin polymers

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Application Number Priority Date Filing Date Title
US556482A US3024227A (en) 1955-12-30 1955-12-30 Low pressure process for production of olefin polymers with a peroxide containing catalyst
US144857A US3152089A (en) 1955-12-30 1961-10-13 Catalyst for production of olefin polymers

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US3152089A true US3152089A (en) 1964-10-06

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US (1) US3152089A (enrdf_load_stackoverflow)
CH (1) CH361919A (enrdf_load_stackoverflow)
FR (1) FR1169630A (enrdf_load_stackoverflow)
GB (1) GB832083A (enrdf_load_stackoverflow)
IT (1) IT564176A (enrdf_load_stackoverflow)
NL (2) NL213365A (enrdf_load_stackoverflow)

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JPS6042404A (ja) * 1983-08-16 1985-03-06 Sumitomo Chem Co Ltd オレフインの重合方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2482877A (en) * 1946-05-31 1949-09-27 Universal Oil Prod Co Polymerization of ethylene
US2762791A (en) * 1953-09-24 1956-09-11 Du Pont Ethylene polymerization
US2822357A (en) * 1955-01-28 1958-02-04 Du Pont Manufacture of polyethylene of controlled molecular weight
US2905645A (en) * 1954-08-16 1959-09-22 Du Pont Polymerization catalysts

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2482877A (en) * 1946-05-31 1949-09-27 Universal Oil Prod Co Polymerization of ethylene
US2762791A (en) * 1953-09-24 1956-09-11 Du Pont Ethylene polymerization
US2905645A (en) * 1954-08-16 1959-09-22 Du Pont Polymerization catalysts
US2822357A (en) * 1955-01-28 1958-02-04 Du Pont Manufacture of polyethylene of controlled molecular weight

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NL213365A (enrdf_load_stackoverflow)
NL94901C (enrdf_load_stackoverflow)
IT564176A (enrdf_load_stackoverflow)
CH361919A (fr) 1962-05-15
FR1169630A (fr) 1958-12-31
GB832083A (en) 1960-04-06

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